Thorough discussion on how surface modification and self-assembly play roles in the atomically precise formation and property tailoring of molecular clusters
Atomically Precise Metal Clusters: Surface Engineering and Hierarchical Assembly summarizes and discusses the surface modification, assembly, and property tailoring of a wide variety of nanoclusters, including the well-explored metal clusters, addressing the structure-property relationships throughout. The atomic-level control in synthesis, new types of structures, and physical/chemical properties of nanoclusters are illustrated in various chapters.
The controlled modification and assembly of metal nanoclusters is expected to have a major impact on future nanoscience research and other areas, with distinctive metal cluster-based function materials with precise structures uncovering exciting opportunities in both fundamental research and practical applications.
Written by a highly qualified academic with significant research experience in the field, Atomically Precise Metal Clusters includes information on: - Ligand engineering and assembly of coinage metal nanoclusters such as gold, silver, and copper- Recent advances in post-modification of polyoxometalates and small transition metal chalcogenide superatom clusters- Synthesis and assembly of cadmium chalcogenide supertetrahedral clusters and modification and assembly of Fe-S clusters- Indium phosphide magic-sized clusters, ligand-tailoring platinum and palladium clusters, and metal oxo clusters (MOCs)- Enabling access to desired functions in metal clusters for catalysis, optics, biomedicine, and other fields through surface engineering and supramolecular assembly
A timely and comprehensive book that summarizes the recent progress in the surface modification and self-assembly of metal nanoclusters, Atomically Precise Metal Clusters provides essential guidance for graduate students and advanced researchers in material science, chemistry, biomedicine, and other disciplines.
Table of Contents
Preface xi
Abbreviations xiii
1 Property Tailoring of Gold Clusters via Surface Engineering and Supramolecular Assembly 1
1.1 Introduction 1
1.2 Surface Modification of Gold NCs 2
1.2.1 Ligand Exchange 2
1.2.1.1 Thiolate/Selenolate as Incoming Ligands 2
1.2.1.2 Alkynyl as Incoming Ligands 3
1.2.1.3 N-Heterocyclic Carbenes (NHCs) as Incoming Ligands 5
1.2.2 Surface Locking Through Coordination 6
1.2.3 Post-Assembly Surface Modification 7
1.3 Gold Cluster-Assembled Materials (GCAMs) 8
1.3.1 1D Cluster Arrays Bridged by Metal-Metal Bonds 9
1.3.2 Covalently Bridged Oligomers and Networks 10
1.4 Applications 13
1.4.1 Biomedical Application 14
1.4.2 Semiconductivity 16
1.4.3 Magnetism 17
1.5 Conclusion 18
References 18
2 Modification and Assembly of Atomically Precise Silver Clusters 23
2.1 Introduction 23
2.2 Precise Modification of Discrete Silver Clusters 23
2.2.1 Modification by Supramolecular Interactions 24
2.2.2 Modification by Functionalizing and Protecting Ligand 26
2.2.2.1 Substitution of Labile Solvent Molecules 26
2.2.2.2 Modulating Weakly Coordinated Non-S Auxiliary Ligands 27
2.2.2.3 Replacing Coordinated S-containing Ligand by Other Functional S-containing Ligands 32
2.3 Assembly of Silver Clusters into Atomically Precise Extended Structures 39
2.3.1 Supramolecular Assembly of Silver Clusters 39
2.3.2 Coordination Assembly of Silver Clusters 42
2.3.2.1 Inorganic Ion Linkers 42
2.3.2.2 POMs Linkers 44
2.3.2.3 Organic Bi/Multidentate Linkers 45
2.4 Applications 54
2.4.1 Luminescent Switching and Sensing Oxygen and VOCs 54
2.4.2 Ratiometric Luminescent Temperature Sensing 56
2.4.3 Catalytic Properties 57
2.5 Conclusion and Perspectives 58
References 59
3 Modification and Assembly of Copper Clusters 65
3.1 Introduction 65
3.2 Synthesis and Properties of Cu Clusters 66
3.3 Modification and Assembly of Copper Clusters 68
3.3.1 Thiolates Ligands Modified Copper Clusters 68
3.3.2 Phosphine Ligands Modified Cu Clusters 74
3.3.3 Alkynyl Ligands Modified Copper Clusters 77
3.3.4 Other Ligands Modified Copper Cluster 82
3.3.5 Assembly of Copper Clusters 84
3.4 Conclusion and Perspectives 85
References 85
4 Recent Advances in Post-Modification of Polyoxometalates: Structures and Properties 93
4.1 Introduction 93
4.2 Synthetic Strategies and Structural Overviews 94
4.2.1 Surfactant-Encapsulated POM Clusters 95
4.2.2 Assembly of Janus POM-POSS Co-clusters 101
4.2.3 Porous POM-Based Metal-Organic Framework (MOF) Materials 102
4.3 Applications 107
4.3.1 POM-Based Nanostructures for Asymmetric Catalysis 107
4.3.2 POM-Based Nanostructures for Electrochemistry and Electrocatalysis 110
4.3.3 POM-Based Nanostructures for Photocatalytic 117
4.3.4 POM-Based Nanostructures for Biological Applications 119
4.4 Conclusion and Perspectives 122
References 123
5 Small Transition Metal Chalcogenide Superatom Clusters 131
5.1 Introduction 131
5.2 Synthesis and Properties of M 6 E 8 L 6 Superatoms 132
5.2.1 Synthesis of M 6 E 8 L 6 Superatoms 132
5.2.1.1 Gas-Phase Synthesis 132
5.2.1.2 Solution-Phase Synthesis 133
5.2.1.3 Solid-Phase Synthesis 133
5.2.2 Properties of M 6 E 8 L 6 Superatoms 133
5.3 Modification and Assembly of M 6 E 8 L 6 Superatoms 134
5.3.1 Modification of Superatoms 134
5.3.1.1 Functionalized Superatoms 134
5.3.1.2 Site-Differentiated Superatoms 135
5.3.2 Assembly of Superatoms 137
5.3.2.1 Discrete Bridged and Fused Oligomers of Superatoms 137
5.3.2.2 Supermolecule Assembly 138
5.3.2.3 Covalent Superatomic Crystals 142
5.4 Collective Properties of Superatomic Crystals 145
5.4.1 Electrochemical Properties, Single-Electron Currents, and Electronic Transport 145
5.4.2 Thermal Transport 148
5.5 Conclusion and Perspectives 151
References 151
6 Synthesis and Assembly of Cadmium Chalcogenide Supertetrahedral Clusters 157
6.1 Introduction 157
6.2 Synthesis and Structure of Cadmium Chalcogenide Supertetrahedral Clusters 158
6.2.1 Tn-Type Clusters 158
6.2.2 Pn-Type Clusters 160
6.2.3 Cn-Type Clusters 161
6.3 Assembly of Cadmium Chalcogenide Supertetrahedral Clusters 163
6.3.1 Inorganic Open Frameworks 163
6.3.2 Organic Open Frameworks 169
6.3.2.1 N-Donor Ligands 169
6.3.2.2 Other Organic Ligands 175
6.4 Properties 176
6.4.1 Photoluminescent Properties 176
6.4.2 Photodegradation of Organic Dyes 178
6.5 Conclusion and Perspectives 179
References 180
7 The Modification and Assembly of Fe-S Clusters 185
7.1 Introduction 185
7.2 The Modification of the First and Second Coordination Sphere on Fe-S Clusters 187
7.2.1 The Modification of the First Coordination Sphere by Phosphine Ligands 187
7.2.2 The Modification of the First Coordination Sphere by NHC and Chelated N-Based Ligands 189
7.2.3 The Modification of the Second Coordination Sphere by Aliphatic Dithiolate Bridged Ligands 190
7.2.4 The Modification of the Second Coordination Sphere by Aromatic Dithiolate Bridged Ligands 191
7.2.5 The Modification of the First and Second Coordination Sphere by Photosensitive Ligands 193
7.3 The Assembly of Fe-S Clusters 195
7.3.1 The Assembly of Fe-S Clusters to Form Polynuclear Fe-S Complexes 195
7.3.2 The Assembly of Fe-S Clusters to Form CPs 195
7.3.3 The Assembly of Fe-S Clusters Anchored Onto Heterogeneous Supports 198
7.4 The Application of [2Fe2S] Clusters in Photocatalytic H 2 Production 202
7.5 Conclusion and Perspective 206
References 206
8 Indium Phosphide Magic-Sized Clusters 217
8.1 Introduction 217
8.2 Synthesis of InP MSCs 218
8.2.1 The Low Temperature Method 219
8.2.2 The Ligands Method 220
8.2.3 The Doping Method 223
8.3 Growth of InP QDs from InP MSCs 228
8.3.1 The Synthesis Methods from InP MSCs to InP QDs 228
8.3.2 The Influence on the Synthesis of InP MSCs to InP QDs 230
8.3.3 The Synthesis Mechanism from InP MSCs to InP QDs 233
8.4 Other Applications of InP MSCs 235
8.4.1 The Synthesis of Diverse Morphology in InP Nanostructures 235
8.4.2 Developing the Luminescent Property of InP MSCs 236
8.5 Conclusion and Perspectives 237
References 238
9 Ligand-Tailoring Platinum and Palladium Clusters 241
9.1 Introduction 241
9.2 Synthesis of Platinum and Palladium Clusters 242
9.2.1 Synthesis of Pt/Pd Carbonyl Clusters (PCCs) 242
9.2.1.1 Direct Carbonylation Method 242
9.2.1.2 Redox-Induced Methods 244
9.2.1.3 Chemically/Physically Induced Methods 245
9.2.2 Synthesis of Pt/Pd-Clusters Protected by Organic Ligands 247
9.3 Ligand Regulation and Modification of Platinum and Palladium Clusters 255
9.3.1 Ligand-Tailoring and Assembly of Platinum Clusters 255
9.3.2 Modification of Palladium Clusters 260
9.4 Conclusion and Perspectives 262
References 263
10 Metal Oxo Clusters 271
10.1 Introduction 271
10.2 Structure and Properties of Zirconium Oxo Clusters (ZrOCs) 272
10.2.1 Formation of Zr Oxo Cluster in Aqueous Medium 273
10.2.2 Formation of Zr Oxo Clusters in Organic Medium 275
10.3 Structure and Properties of Titanium Oxo Clusters (TiOCs) 278
10.3.1 Structural Diversity of Titanium Oxo Clusters 278
10.3.1.1 Carboxylate Ligands-Stabilized Titanium Oxo Clusters 279
10.3.1.2 Phosphonate-Stabilized Titanium Oxo Clusters 280
10.3.1.3 N-Donor Ligands Participating in Titanium Oxo Clusters 281
10.3.2 Bandgap Engineering of Titanium Oxo Clusters 283
10.3.2.1 Ligand Modification 283
10.3.2.2 Metallic Doping 283
10.4 Structure and Properties of Lanthanide Oxo Clusters (LnOCs) 287
10.4.1 Synthetic Strategy for High-Nuclearity Lanthanide Clusters 287
10.4.1.1 Ligand-Controlled Hydrolysis Approach 288
10.4.1.2 Anion Template Method 289
10.4.1.3 Slow Release of Anion Templates 289
10.4.1.4 Multiple Anion Templates, Including Mixed Templating Anions 290
10.4.2 Building Blocks for the Assembly of High-Nuclearity Lanthanide Clusters 292
10.5 Conclusion and Perspective 294
References 294
Index 301
